CN1986923A - New two-step water phase suspending process for preparing polyacrylonitrile fibril for carbon fiber - Google Patents
New two-step water phase suspending process for preparing polyacrylonitrile fibril for carbon fiber Download PDFInfo
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- CN1986923A CN1986923A CN 200610070589 CN200610070589A CN1986923A CN 1986923 A CN1986923 A CN 1986923A CN 200610070589 CN200610070589 CN 200610070589 CN 200610070589 A CN200610070589 A CN 200610070589A CN 1986923 A CN1986923 A CN 1986923A
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- polyacrylonitrile
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Abstract
The two-step water phase suspending process of preparing polyactylonitrile fibril for carbon fiber includes the key steps of: continuous polymerization in polymerizing solution with ammonium persulfate to prepare high stability polyactylonitrile powder; and dissolving polyactylonitrile powder in dimethyl sulfoxide as solvent and dry spraying and wet spinning to obtain polyactylonitrile fibril. The polyactylonitrile fibril has the features of good crystallizing performance, narrow molecular weight distribution, stable quality, etc. and may be used in producing carbon fiber with tensile strength over 4900 MPa. The process of the present invention is suitable for producing high performance polyactylonitrile fibril in industrial scale.
Description
(1) technical field
The invention belongs to the high-performance fiber technical field, be particularly suitable for the production of high performance carbon fiber used polyacrylonitrile precursor.
(2) technical background
The application of high-performance carbon fibre is very extensive, has been penetrated into sports equipment, amusement and leisure at present, tourist facilities, automobile component, train part, aircraft manufacturing, electric power, oil, chemical industry, navigation, biomedicine, a plurality of fields such as building, strategic missile, bulletproof armour are described as the most vital new material of 21st century.
The main raw material of high-strength carbon fiber is a polyacrylonitrile fibril.The domestic production polyacrylonitrile fibril for carbon fiber all adopts one-step method at present, be about to acrylonitrile and second, third condensate and dimethyl formamide, nitric acid or sodium sulfocyanate equal solvent join in the reactor together and mix, forming the spinning solution that contains certain polyacrylonitrile through polymerization behind the certain hour under uniform temperature and the atmosphere, eyelet by spinneret cap is directly injected to stoste and prepares polyacrylonitrile fibril in the coagulation bath then, and this is the one-step method wet spinning.Utilizing this method to prepare polyacrylonitrile fibril yields poorly, quality control difficulty in the polymerization process is easy to occur gel in the production process, thereby can cause the instability of precursor performance, the carbon fiber strength that the polyacrylonitrile fibril that utilizes wet spinning to prepare is fired is lower, generally is no more than 3500Mpa.
High performance carbon fiber used polyacrylonitrile precursor production technology is by Japan, the U.S., Germany, a few enterprise such as France and China Taiwan grasps, because high-performance carbon fibre is military significant, external polyacrylonitrile fibril production technology, prescription, technology etc. are externally not open, though a small amount of technology report is arranged, technology is identical with domestic cardinal principle, on solution formula, be acrylonitrile, azodiisobutyronitrile, comonomers such as itaconic acid are at dimethyl sulfoxide (DMSO), dimethyl formamide, organic solvent or nitric acid such as dimethylacetylamide, direct polymerization forms polyacrylonitrile solution in the inorganic solvents such as sodium sulfocyanate, utilizes this solution spinning polyacrylonitrile fibril then.It is very high with the utilization requirement to solvent recovery to utilize such medium and method to prepare polyacrylonitrile spinning solution, deals with improperly to cause environmental pollution.
(3) summary of the invention
At present polyacrylonitrile fibril for carbon fiber large-scale production difficulty; quality stability is poor, and performance is not high, and polymerisation medium has deficiencies such as pollution; the present invention proposes water as polymerisation medium, adopt two-step water phase suspending to prepare the new method of polyacrylonitrile fibril for carbon fiber.
Two-step water phase suspending of the present invention prepares the polyacrylonitrile fibril for carbon fiber new method, it is characterized in that the first step is a medium with deionized water earlier, adopt the aqueous-phase suspending continuous polymerization technique to prepare the polyacrylonitrile powder, second step was used dmso solution polyacrylonitrile powder, the preparation spinning solution adopts dry-jet wet spinning process, is about to polyacrylonitrile spinning solution, by behind the eyelet of spinneret cap earlier through one section air layer, and then be ejected into and prepare polyacrylonitrile fibril for carbon fiber in the coagulation bath.
Two-step water phase suspending of the present invention prepares the polyacrylonitrile fibril for carbon fiber new method, when the first step prepares the polyacrylonitrile powder, with acrylonitrile 20～50%, ammonium persulfate 2～8%, deionized water 78～42% is formed polymeric solution, feeds polymeric kettle continuously and carries out polymerization, the polymeric kettle temperature is 50-70 ℃, polymerization time 40-90 minute, obtain polymeric solution, will make the polyacrylonitrile powder after the polymeric solution washing oven dry.
Two-step water phase suspending of the present invention prepares the polyacrylonitrile fibril for carbon fiber new method, when second step dissolving polyacrylonitrile powder, utilize dimethyl sulfoxide (DMSO) as solvent, solution temperature is 40-70 ℃, dimethyl sulfoxide (DMSO) concentration 70-95%, polyacrylonitrile powder concentration 30-5%, dissolving mixing speed 20-150rpm, dissolution time 5-10 hour, spinning solution after the dissolving prepares polyacrylonitrile fibril through adopting dry-jet wet spinning process after the deaeration, be that spinning solution sprays into an air layer earlier by the spinneret orifice on the spinneret cap, air layer thickness 5-15mm, and then enter body lotion in the coagulating tank, the coagulation bath temperature is 5-15 ℃, and the concentration of dimethyl sulfoxide (DMSO) is 30-70% in the coagulation bath, and the speed of spinning solution when spinneret cap sprays is per minute 5-30 rice.
The polyacrylonitrile as-spun fibre that makes from coagulating bath is again through making polyacrylonitrile fibril after multiple tracks washing and the drawing-off.
Utilize the present invention to prepare polyacrylonitrile fibril for carbon fiber, spinning speed is fast, the output height, and the filament surfaces defective is few, and polymerisation medium is pollution-free, and the carbon fiber strength that utilizes precursor of the present invention to fire to obtain surpasses 4900MPa, has reached the high-performance carbon fibre index.
(4) specific embodiment
Embodiment 1
Acrylonitrile monemer solution is injected polymeric kettle by gear pump according to 20% ratio, ammonium persulfate is added polymeric kettle according to 2% ratio, deionized water is injected polymeric kettle by measuring pump according to 78% ratio, keep 70 ℃ of temperature in the polymeric kettle, the slurry that contains the polyacrylonitrile powder is discharged polymeric kettle continuously, makes the polyacrylonitrile powder after filtering, wash, drying.The polyacrylonitrile powder that makes in being housed, the dissolution kettle of hot dimethyl sulfoxide (DMSO) is dissolved, solution temperature is 40 ℃, sulfoxide concentration 70%, polyacrylonitrile powder concentration is 30%, dissolution kettle agitator speed 20rpm, dissolution time 10 hours, spinning solution after the dissolving is through deaeration, utilize measuring pump metering back to spray into a 15mm air layer earlier by the spinneret orifice on the spinneret cap, by in the body lotion in the directive wheel importing coagulating tank, the coagulation bath temperature is 5 ℃ then, the concentration of dimethyl sulfoxide (DMSO) is 70% in the coagulation bath, other are deionized water, and content 30%, the spinning solution speed when spinneret cap sprays is 5 meters of per minutes.The nascent polyacrylonitrile fibre that makes from coagulating bath is again through making the polyacrylonitrile fibril of fiber number 1.2dtex after washing of 4 roads and the 4 road drawing-offs.
Make carbon fiber strength after utilizing this precursor to handle and be 4980Mpa through warm carbonization in 180-280 ℃ of pre-oxidation and 800 ℃ and 1500 ℃ of high temperature cabonizations.
Embodiment 2
Acrylonitrile monemer solution is injected polymeric kettle by gear pump according to 35% ratio, ammonium persulfate is added polymeric kettle according to 5% ratio, deionized water is injected polymeric kettle by measuring pump according to 60% ratio, keep 60 ℃ of temperature in the polymeric kettle, the slurry that contains the polyacrylonitrile powder is discharged polymeric kettle continuously, makes the polyacrylonitrile powder after filtering, wash, drying.The polyacrylonitrile powder that makes in being housed, the dissolution kettle of hot dimethyl sulfoxide (DMSO) is dissolved, solution temperature is 55 ℃, sulfoxide concentration 85%, polyacrylonitrile powder concentration is 15%, dissolution kettle agitator speed 80rpm, dissolution time 8 hours, spinning solution after the dissolving utilizes measuring pump metering back to spray into a 10mm air layer earlier by the spinneret orifice on the spinneret cap, then by in the body lotion in the directive wheel importing coagulating tank, the coagulation bath temperature is 10 ℃, and the concentration of dimethyl sulfoxide (DMSO) is 50% in the coagulation bath, and other are deionized water, content 50%, the spinning solution speed when spinneret cap sprays is 20 meters of per minutes.The nascent polyacrylonitrile fibre that makes from coagulating bath is again through making the polyacrylonitrile fibril of fiber number 1.2dtex after washing of 4 roads and the 4 road drawing-offs.
Make carbon fiber strength after utilizing this precursor to handle and be 5030Mpa through warm carbonization in 180-280 ℃ of pre-oxidation and 800 ℃ and 1500 ℃ of high temperature cabonizations.
Embodiment 3
Acrylonitrile monemer solution is injected polymeric kettle by gear pump according to 50% ratio, ammonium persulfate is added polymeric kettle according to 8% ratio, deionized water is injected polymeric kettle by measuring pump according to 42% ratio, keep 50 ℃ of temperature in the polymeric kettle, the slurry that contains the polyacrylonitrile powder is discharged polymeric kettle continuously, makes the polyacrylonitrile powder after filtering, wash, drying.The polyacrylonitrile powder that makes is dissolved in the dissolution kettle that hot dimethyl sulfoxide (DMSO) is housed dissolves, solution temperature is 70 ℃, sulfoxide concentration 95%, polyacrylonitrile powder concentration is 5%, dissolution kettle agitator speed 150rpm, dissolution time 5 hours, spinning solution after the dissolving utilizes measuring pump metering back to spray into a 5mm air layer earlier by the spinneret orifice on the spinneret cap, then by in the body lotion in the directive wheel importing coagulating tank, the coagulation bath temperature is 15 ℃, and the concentration of dimethyl sulfoxide (DMSO) is 30% in the coagulation bath, and other are deionized water, content 70%, the spinning solution speed when spinneret cap sprays is 30 meters of per minutes.The nascent polyacrylonitrile fibre that makes from coagulating bath is again through making the polyacrylonitrile fibril of fiber number 1.2dtex after washing of 4 roads and the 4 road drawing-offs.
Make carbon fiber strength after utilizing this precursor to handle and be 4950Mpa through warm carbonization in 180-280 ℃ of pre-oxidation and 800 ℃ and 1500 ℃ of high temperature cabonizations.
Claims (4)
1, two-step water phase suspending prepares the polyacrylonitrile fibril for carbon fiber new method, it is characterized in that the first step prepares the polyacrylonitrile powder with the aqueous-phase suspending continuous polymerization technique, second step adopted dry-jet wet spinning process to prepare polyacrylonitrile fibril for carbon fiber with dmso solution polyacrylonitrile powder.
2, two-step water phase suspending according to claim 1 prepares the polyacrylonitrile fibril for carbon fiber new method, it is characterized in that with acrylonitrile 20～50%, ammonium persulfate 2～8%, deionized water 78～42% is formed polymeric solution, feed polymeric kettle continuously and carry out polymerization, the polymeric kettle temperature is 50-70 ℃, polymerization time 40-90 minute, obtain polymeric solution, will make the polyacrylonitrile powder after the polymeric solution washing oven dry.
3, two-step water phase suspending according to claim 1 prepares the polyacrylonitrile fibril for carbon fiber new method, utilize dimethyl sulfoxide (DMSO) as solvent when it is characterized in that dissolving the polyacrylonitrile powder, solution temperature is 40-70 ℃, sulfoxide concentration 70-95%, polyacrylonitrile powder concentration 30-5%, dissolving mixing speed 20-150rpm, dissolution time 5-10 hour.
4, two-step water phase suspending according to claim 1 prepares the polyacrylonitrile fibril for carbon fiber new method, spinning solution after it is characterized in that dissolving is through after the deaeration, adopt dry-jet wet spinning process to prepare polyacrylonitrile fibril, the air layer thickness 5-15mm of dry-jet wet spinning process, 5-15 ℃ of coagulation bath temperature, the concentration 30-70% of dimethyl sulfoxide (DMSO) in the coagulation bath, the spinning solution speed when spinneret cap sprays is per minute 5-30 rice.
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| CN 200610070589 CN1986923A (en) | 2006-12-07 | 2006-12-07 | New two-step water phase suspending process for preparing polyacrylonitrile fibril for carbon fiber |
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| CN 200610070589 CN1986923A (en) | 2006-12-07 | 2006-12-07 | New two-step water phase suspending process for preparing polyacrylonitrile fibril for carbon fiber |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724922B (en) * | 2009-11-26 | 2012-09-05 | 中复神鹰碳纤维有限责任公司 | Method for preparing high-strength polyacrylonitrile-based precursor for carbon fiber |
| CN106169364A (en) * | 2016-07-28 | 2016-11-30 | 郑洪华 | A kind of three winding single-circuit transformer and manufacture method thereof |
| CN106205990A (en) * | 2016-07-28 | 2016-12-07 | 郑洪华 | A kind of high reliability neutralizing transformer and manufacture method thereof |
| CN106409490A (en) * | 2016-08-24 | 2017-02-15 | 宁波华众和创工业设计有限公司 | Low-loss and high-efficiency autotransformer and production method thereof |
| CN106486278A (en) * | 2016-08-24 | 2017-03-08 | 宁波华众和创工业设计有限公司 | A kind of Large Copacity single-circuit transformer and its manufacture method |
| CN113174657A (en) * | 2021-04-07 | 2021-07-27 | 山东大学 | Preparation method and application of graphene-doped carbon fiber |
-
2006
- 2006-12-07 CN CN 200610070589 patent/CN1986923A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724922B (en) * | 2009-11-26 | 2012-09-05 | 中复神鹰碳纤维有限责任公司 | Method for preparing high-strength polyacrylonitrile-based precursor for carbon fiber |
| CN106169364A (en) * | 2016-07-28 | 2016-11-30 | 郑洪华 | A kind of three winding single-circuit transformer and manufacture method thereof |
| CN106205990A (en) * | 2016-07-28 | 2016-12-07 | 郑洪华 | A kind of high reliability neutralizing transformer and manufacture method thereof |
| CN106409490A (en) * | 2016-08-24 | 2017-02-15 | 宁波华众和创工业设计有限公司 | Low-loss and high-efficiency autotransformer and production method thereof |
| CN106486278A (en) * | 2016-08-24 | 2017-03-08 | 宁波华众和创工业设计有限公司 | A kind of Large Copacity single-circuit transformer and its manufacture method |
| CN113174657A (en) * | 2021-04-07 | 2021-07-27 | 山东大学 | Preparation method and application of graphene-doped carbon fiber |
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Open date: 20070627 |